The availability of glycerol is rapidly increasing due to the expanding biodiesel industry, which produces this polyol as the main waste material. Several value-added chemicals have been synthesized using glycerol as a feedstock; however, the conversion of glycerol to lactic acid has been investigated to a lesser extent despite the numerous and novel uses of lactic acid. We report a family of iridium complexes as the first homogeneous catalysts for the conversion of glycerol to lactic acid. These have higher activity and selectivity than the previously reported heterogeneous systems. In addition, hydrogen gas is generated as a useful byproduct. Unlike prior systems, the reactions can be performed in air, under mild conditions and without solvent. Our method has even been applied to samples of crude glycerol waste derived from the biodiesel industry without prior purification, albeit with somewhat lower activity while maintaining the same high selectivity.
A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a "borrowing hydrogen" reaction. Notably, this reaction is highly selective for the monomethylated product.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.